Solvothermal synthesis of organoclay/Cu-MOF composite and its application in film modified GCE for simultaneous electrochemical detection of deoxyepinephrine, acetaminophen and tyrosine.

An organoclay/copper-based metal-organic framework (MOF) composite was synthesized using a solvothermal method by growing a Cu-BTC (copper(ii) benzene-1,3,5-tricarboxylate) MOF from a mixture of the MOF precursor solution in which various amounts of organoclay had been dispersed. The organoclay was obtained by intercalating a cationic dye, namely thionin, into a natural Cameroonian clay sampled in Sagba deposit (North West of Cameroon). The organoclay and the as-synthesized composites were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and Brunauer, Emmett and Teller (BET) techniques. From Scherrer's equation, the crystallite size of the composite was found to be between 55 and 58 nm, twice as large as the pristine MOF's crystallite size. The organoclay/Cu-MOF composite (Sa-TN50/Cu3(BTC)2) exhibiting a BET surface area of 192 m2 g-1, about twice that of pristine clay and about one seventh that of pristine MOF, was then utilized to form a stable thin film onto glassy carbon electrodes (GCE) by drop coating (Sa-TN50/Cu3(BTC)2/GCE). These electrodes demonstrated electrocatalytic behavior toward deoxyepinephrine (DXEP) and thus enabled selective and simultaneous sensitive detection of three analytes: DXEP, acetaminophen (AC) and tyrosine (TYR) compared with bare GCE and clay modified electrode. Under optimum conditions, Sa-TN50/Cu3(BTC)2/GCE exhibited good performance including large calibration curves ranging from 5.0 µM to 138.0 µM for DXEP, 4.0 µM to 153.0 µM for AC and 1.0 µM to 29.4 µM for TYR. The detection limits were found to be, 0.4 µM, 0.7 µM and 0.2 µM for DXEP, AC and TYR, respectively. The developed sensors have been applied successfully in the quantification of AC in a commercial tablet of AC, and DXEP, AC and TYR in tap water.

Co-Carbonization of Discard Coal with Waste Polyethylene Terephthalate towards the Preparation of Metallurgical Coke.

Waste plastics such as polyethylene terephthalate (w-PET) and stockpiled discard coal (d-coal) pose a global environmental threat as they are disposed of in large quantities as solid waste into landfills and are particularly hazardous due to spontaneous combustion of d-coal that produces greenhouse gases (GHG) and the non-biodegradability of w-PET plastic products. This study reports on the development of a composite material, prepared from w-PET and d-coal, with physical and chemical properties similar to that of metallurgical coke. The w-PET/d-coal composite was synthesized via a co-carbonization process at 700 °C under a constant flow of nitrogen gas. Proximate analysis results showed that a carbonized w-PET/d-coal composite could attain up to 35% improvement in fixed carbon content compared to its d-coal counterpart, such that an initial fixed carbon content of 14-75% in carbonized discard coal could be improved to 49-86% in carbonized w-PET/d-coal composites. The results clearly demonstrate the role of d-coal ash on the degree of thermo-catalytic conversion of w-PET to solid carbon, showing that the yield of carbon derived from w-PET (i.e., c-PET) was proportional to the ash content of d-coal. Furthermore, the chemical and physical characterization of the composition and structure of the c-PET/d-coal composite showed evidence of mainly graphitized carbon and a post-carbonization caking ability similar to that of metallurgical coke. The results obtained in this study show potential for the use of waste raw materials, w-PET and d-coal, towards the development of an eco-friendly reductant with comparable chemical and physical properties to metallurgical coke.

Acylation of Anisole With Benzoyl Chloride Over Rapidly Synthesized Fly Ash-Based HBEA Zeolite.

Stable HBEA zeolite with high surface area and strong acid sites was synthesized from coal fly ash-based silica extract via indirect hydrothermal synthesis. The rapid HBEA hydrothermal crystallization times of 8, 10, and 12 h were achieved through a reduced molar water fraction in the synthesis composition. The HBEA zeolites prepared from fly ash silica extract exhibited well-defined spheroidal-shaped crystal morphology with uniform particle sizes of 192, 190, or 239 nm obtained after 8, 10, or 12 h of synthesis time, respectively. The high surface area and the microporous area of 702 and 722 m2/g were achieved as a function of shorter hydrothermal synthesis durations (10 and 24 h, respectively) compared to 48 or 72 h, which resulted in HBEA zeolites with lower surface areas of 538 and 670 m2/g. Likewise, temperature-programmed desorption measurements of fly ash-based HBEA zeolites revealed the presence of weak and strong acid sites in the zeolite. The submicron crystal sizes with a well-defined porosity of HBEA zeolites enhanced the diffusion of anisole and benzoyl chloride molecules toward the active acid sites and hence showed better conversion and selectivity in acylation products. High conversion of benzoyl chloride with anisole was achieved, reaching up to 83% with a 93-96% selectivity toward 4-methoxyacetophenone.

Microwave Irradiation-Assisted Synthesis of Zeolites from Coal Fly Ash: An Optimization Study for a Sustainable and Efficient Production Process.

Class F South African coal fly ash was used as a precursor for the synthesis of zeolite A via complete microwave irradiation. To attain optimal conditions for the synthesis of zeolite A with minimum impurities, the microwave synthesis time, irradiation power, and Si/Al ratio were varied. Sodalite with fly ash phases were obtained when the Si/Al ratio in the coal fly ash was not adjusted and when the microwave irradiated coal fly ash slurry was used instead of the extract solution. Increased microwave irradiation time power and time favored the crystallization of zeolite A phase due to sufficient energy needed to ensure the dissolution of Al and Si from coal fly ash. A Brunauer-Emmett-Teller surface area of 29.54 m2/g and a cation exchange capacity of 3.10 mequiv/g were achieved for zeolite A, suggesting its potential application as an adsorbent and cation exchange material for environmental remediation. Complete microwave irradiation offers a greener approach toward zeolite synthesis from coal fly ash compared to conventional hydrothermal and fusion methods that consume a lot of energy and require longer reaction times.

Experimental Demonstration of Dynamic Temperature-Dependent Behavior of UiO-66 Metal-Organic Framework: Compaction of Hydroxylated and Dehydroxylated Forms of UiO-66 for High-Pressure Hydrogen Storage.

High-pressure (700 MPa or ∼100 000 psi) compaction of dehydroxylated and hydroxylated UiO-66 for H2 storage applications is reported. The dehydroxylation reaction was found to occur between 150 and 300 °C. The H2 uptake capacity of powdered hydroxylated UiO-66 reaches 4.6 wt % at 77 K and 100 bar, which is 21% higher than that of dehydroxylated UiO-66 (3.8 wt %). On compaction, the H2 uptake capacity of dehydroxylated UiO-66 pellets reduces by 66% from 3.8 to 1.3 wt %, while for hydroxylated UiO-66 the pellets show only a 9% reduction in capacity from 4.6 to 4.2 wt %. This implies that the H2 uptake capacity of compacted hydroxylated UiO-66 is at least three times higher than that of dehydroxylated UiO-66, and therefore, hydroxylated UiO-66 is more promising for hydrogen storage applications. The H2 uptake capacity is closely related to compaction-induced changes in the porosity of UiO-66. The effect of compaction is greatest in partially dehydroxylated UiO-66 samples that are thermally treated at 200 and 290 °C. These compacted samples exhibit XRD patterns indicative of an amorphous material, low porosity (surface area reduces from between 700 and 1300 m2/g to ca. 200 m2/g and pore volume from between 0.4 and 0.6 cm3/g to 0.1 and 0.15 cm3/g), and very low hydrogen uptake (0.7-0.9 wt % at 77 K and 100 bar). The observed activation-temperature-induced dynamic behavior of UiO-66 is unusual for metal-organic frameworks (MOFs) and has previously only been reported in computational studies. After compaction at 700 MPa, the structural properties and H2 uptake of hydroxylated UiO-66 remain relatively unchanged but are extremely compromised upon compaction of dehydroxylated UiO-66. Therefore, UiO-66 responds in a dynamic manner to changes in activation temperature within the range in which it has hitherto been considered stable.

Onion-derived activated carbons with enhanced surface area for improved hydrogen storage and electrochemical energy application.

High surface area activated carbons (ACs) were prepared from a hydrochar derived from waste onion peels. The resulting ACs had a unique graphene-like nanosheet morphology. The presence of N (0.7%) and O content (8.1%) in the OPAC-800 °C was indicative of in situ incorporation of nitrogen groups from the onion peels. The specific surface area and pore volume of the best OPAC sample was found to be 3150 m2 g-1 and 1.64 cm3 g-1, respectively. The hydrogen uptake of all the OPAC samples was established to be above 3 wt% (at 77 K and 1 bar) with the highest being 3.67 wt% (800 °C). Additionally, the OPAC-800 °C achieved a specific capacitance of 169 F g-1 at a specific current of 0.5 A g-1 and retained a capacitance of 149 F g-1 at 5 A g-1 in a three electrode system using 3 M KNO3. A symmetric supercapacitor based on the OPAC-800 °C//OPAC-800 °C electrode provided a capacitance of 158 F g-1 at 0.5 A g-1. The maximum specific energy and power was found to be 14 W h kg-1 and 400 W kg-1, respectively. Moreover, the device exhibited a high coulombic efficiency of 99.85% at 5 A g-1 after 10 000 cycles. The results suggested that the high surface area graphene-like carbon nanostructures are excellent materials for enhanced hydrogen storage and supercapacitor applications.

Polymer-Based Shaping Strategy for Zeolite Templated Carbons (ZTC) and Their Metal Organic Framework (MOF) Composites for Improved Hydrogen Storage Properties.

Porous materials such as metal organic frameworks (MOFs), zeolite templated carbons (ZTC), and some porous polymers have endeared the research community for their attractiveness for hydrogen (H2) storage applications. This is due to their remarkable properties, which among others include high surface areas, high porosity, tunability, high thermal, and chemical stability. However, despite their extraordinary properties, their lack of processability due to their inherent powdery nature presents a constraining factor for their full potential for applications in hydrogen storage systems. Additionally, the poor thermal conductivity in some of these materials also contributes to the limitations for their use in this type of application. Therefore, there is a need to develop strategies for producing functional porous composites that are easy-to-handle and with enhanced heat transfer properties while still retaining their high hydrogen adsorption capacities. Herein, we present a simple shaping approach for ZTCs and their MOFs composite using a polymer of intrinsic microporosity (PIM-1). The intrinsic characteristics of the individual porous materials are transferred to the resulting composites leading to improved processability without adversely altering their porous nature. The surface area and hydrogen uptake capacity for the obtained shaped composites were found to be within the range of 1,054-2,433 m2g-1 and 1.22-1.87 H2 wt. %, respectively at 1 bar and 77 K. In summary, the synergistic performance of the obtained materials is comparative to their powder counterparts with additional complementing properties.

Preparation of carbon nanofibers/tubes using waste tyres pyrolysis oil and coal fly ash derived catalyst.

In this study, two waste materials namely; coal fly ash (CFA) and waste tyres pyrolysis oil, were successfuly utilized in the synthesis of carbon nanofibers/tubes (CNF/Ts). In addition, Fe-rich CFA magnetic fraction (Mag-CFA) and ethylene gas were also used for comparison purposes. The carbons obtained from CFA were found to be anchored on the surface of the cenosphere and consisted of both CNTs and CNFs, whereas those obtained from Mag-CFA consisted of only multi-walled carbon nanotubes (MWCNTs). The study further showed that the type of carbon precursor and support material played an important role in determining the nanocarbon growth mechanism. The findings from this research have demonstrated that it is possible to utilize waste tyres pyrolysis oil vapor as a substitute for some expensive commercial carbonaceous gases.

Utilization of waste tyres pyrolysis oil vapour in the synthesis of Zeolite Templated Carbons (ZTCs) for hydrogen storage application.

In this study, we investigated the potential for use of waste tyre pyrolysis oil vapour as a carbon precursor in the synthesis of zeolite templated carbons (ZTC). With Zeolite 13X as the template, the ZTCs were synthesised using two methods namely: 1-step process which involved the carbonization of gaseous carbon precursor in the zeolite template (in this case, ethylene and pyrolysis oil vapour) and the 2-step synthesis method involved the impregnation of zeolite pores with furfural alcohol prior to carbonization of the gaseous carbon precursor. The replication of the zeolite 13X structural ordering was successful using both methods. The 2-step synthesized ZTCs were found to possess the highest specific surface area (3341 m2 g-1) and also had the highest H2 storage capacity (2.5 wt.%). The study therefore confirmed an additional novel strategy for value-addition of waste tyre pyrolysis by-products.

Synthesis of zeolite NaA membrane from fused fly ash extract.

Zeolite-NaA membranes were synthesized from an extract of fused South African fly ash on a porous titanium support by a secondary growth method. The influence of the synthesis molar regime on the formation of zeolite NaA membrane layer was investigated. Two synthesis mixtures were generated by adding either aluminium hydroxide or sodium aluminate to the fused fly ash extract. The feedstock material and the synthesized membranes were characterized by X-diffraction (XRD), scanning electron microscopy (SEM) and X-ray fluorescence spectroscopy (XRF). It was found by XRD and SEM that the cubic crystals of a typical zeolite NaA with a dense intergrown layer was formed on the porous Ti support. The study shows that the source of Al used had an effect on the membrane integrity as sodium aluminate provided the appropriate amount of Na(+) to form a coherent membrane of zeolite NaA, whereas aluminium hydroxide did not. Morphological, the single hydrothermal stage seeded support formed an interlocked array of zeolite NaA particles with neighbouring crystals. Also, a robust, continuous and well-intergrown zeolite NaA membrane was formed with neighbouring crystals of zeolite fused to each other after the multiple stage synthesis. The synthesized membrane was permeable to He (6.0 × 10(6) L m(-2)h(-1) atm(-1)) and CO2 (5.6 × 10(6) L m(-2)h(-1) atm(-1)), which indicate that the layer of the membrane was firmly attached to the porous Ti support. Membrane selectivity was maintained showing membrane integrity with permselectivity of 1.1, showing that a waste feedstock, fly ash, could be utilized for preparing robust zeolite NaA membranes on Ti support.

Leaching and antimicrobial properties of silver nanoparticles loaded onto natural zeolite clinoptilolite by ion exchange and wet impregnation.

This study aimed to compare the leaching and antimicrobial properties of silver that was loaded onto the natural zeolite clinoptilolite by ion exchange and wet impregnation. Silver ions were reduced using sodium borohydride (NaBH4). The leaching of silver from the prepared silver-clinoptilolite (Ag-EHC) nanocomposite samples and their antimicrobial activity on Escherichia coli Epi 300 were investigated. It was observed that the percentage of silver loaded onto EHC depended on the loading procedure and the concentration of silver precursor used. Up to 87% of silver was loaded onto EHC by wet impregnation. The size of synthesized silver nanoparticles varied between 8.71-72.67 nm and 7.93-73.91 nm when silver was loaded by ion exchange and wet impregnation, respectively. The antimicrobial activity of the prepared nanocomposite samples was related to the concentration of silver precursor used, the leaching rate and the size of silver nanoparticles obtained after reduction. However, only in the case of the nanocomposite sample (Ag-WEHC) obtained after loading 43.80 ± 1.90 µg of Ag per gram zeolite through wet impregnation was the leaching rate lower than 0.1 mg L-1 limit recommended by WHO, with an acceptable microbial killing effect.

In situ ultrasonic diagnostic of zeolite X crystallization with novel (hierarchical) morphology from coal fly ash.

In this paper the applicability of an in situ ultrasonic diagnostic technique in understanding the formation process of zeolite X with a novel morphology was demonstrated. The complexity of the starting fly ash feedstock demands independent studies of the formation process for each type of zeolite since it is not known whether the crystallization mechanism will always follow the expected reaction pathway. The hierarchical zeolite X was noted to follow a solution phase-mediated crystallization mechanism which differs from earlier studies of the zeolite A formation process from unaged, clear solution extracted from fused fly ash. The use of the in situ ultrasonic monitoring system provided sufficient data points which enabled closer estimation of the time of transition from the nucleation to the crystal growth step. In order to evaluate the effect of temperature on the resulting in situ attenuation signal, synthesis at three higher temperatures (80, 90 and 94 °C) was investigated. It was shown, by the shift of the US-attenuation signal, that faster crystallization occurred when higher temperatures were applied. The novel hierarchical zeolite X was comprised of intergrown disc-like platelets. It was further observed that there was preferential growth of the disc-shaped platelets of zeolite X crystals in one dimension as the synthesis temperature was increased, allowing tailoring of the hierarchical morphology.

Optimization of hydrothermal synthesis of pure phase zeolite Na-P1 from South African coal fly ashes.

This study was aimed at optimizing the synthesis conditions for pure phase zeolite Na-P1 from three coal fly ashes obtained from power stations in the Mpumalanga province of South Africa. Synthesis variables evaluated were: hydrothermal treatment time (12-48 hours), temperature (100-160°C) and varying molar quantities of water during the hydrothermal treatment step (H(2)O:SiO(2) molar ratio ranged between 0-0.49). The optimum synthesis conditions for preparing pure phase zeolite Na-P1 were achieved when the molar regime was 1 SiO(2): 0.36 Al(2)O(3): 0.59 NaOH: 0.49 H(2)O and ageing was done at 47°C for 48 hours. The optimum hydrothermal treatment time and temperature was 48 hours and 140°C, respectively. Fly ashes sourced from two coal-fired power plants (A, B) were found to produce nearly same high purity zeolite Na-P1 under identical conditions whereas the third fly ash (C) lead to a low quality zeolite Na-P1 under these conditions. The cation exchange capacity for the high pure phase was found to be 4.11 meq/g. These results highlight the fact that adjustment of reactant composition and presynthesis or synthesis parameters, improved quality of zeolite Na-P1 can be achieved and hence an improved potential for application of zeolites prepared from coal fly ash.

Synthesis of hydroxy sodalite from coal fly ash using waste industrial brine solution.

The effect of using industrial waste brine solution instead of ultra pure water was investigated during the synthesis of zeolites using three South African coal fly ashes as Si feedstock. The high halide brine was obtained from the retentate effluent of a reverse osmosis mine water treatment plant. Synthesis conditions applied were; ageing of fly ash was at 47 ° C for 48 hours, and while the hydrothermal treatment temperature was set at 140 ° C for 48 hours. The use of brine as a solvent resulted in the formation of hydroxy sodalite zeolite although unconverted mullite and hematite from the fly ash feedstock was also found in the synthesis product.